Post-CMP treating liquid and method for manufacturing semiconductor device

ABSTRACT

There is disclosed a post-CMP treating liquid comprising water, and resin particles dispersed in the water and having a functional group at a surface thereof, or comprising water, resin particles dispersed in the water, and an additive having a functional group and incorporated in the water. The post-CMP treating liquid exhibits a polishing rate both of an insulating film and a conductive film of 10 nm/min or less.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2002-309608, filed Oct. 24,2002; the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a treating liquid employed in themanufacture of a semiconductor device, and to a method for manufacturinga semiconductor device. In particular, the present invention relates toa treating liquid employed in the post-treatment for Chemical MechanicalPolishing (CMP), and to a method for manufacturing a semiconductordevice using this treating liquid.

2. Description of the Related Art

In recent years, to meet the trend to further enhance the integration ofLSI, the techniques to further refine the wirings are now being rapidlyadvanced in the manufacture of LSIs. Additionally, in order to alleviatethe retardation of wiring RC, it is considered imperative to employ anovel material. Under the circumstances, it is now tried to employ Cuwhich is low in electric resistance (ρ: 1.8 μΩcm) as a conductivematerial, and to employ an insulating film having low relativedielectric constant (k: <2.5) as an electric insulating material.

Cu wirings (wirings made of Cu) are formed, in most cases, as damascenewirings by using a CMP technique. Since an electric conductive materiallocated between wirings can be removed in polishing by a CMP, it ispossible to obtain a wiring relatively free from short-circuits ascompared with the wiring such as the conventional Al wirings formed byRIE.

After this CMP treatment, residual materials such as dust (residualpolishing particles and residual shavings) and unreacted slurryunavoidably remain on the surfaces of the insulating film and of thewirings. These residual materials have been conventionally removed byusing a washing liquid containing a chelate complex-forming agent and asurfactant. However, as the intervals between wirings are increasinglynarrowed, it now becomes more difficult to employ this conventionalmethod for coping with the removal of these residual materials.

Since the intervals of wirings required for the semiconductor device ofthe next generation will be 0.1 μm or less, a small quantity of such avery fine residual material that has been conventionally not consideredto raise any substantial problem may become a cause for the generationof defective wirings, such as short-circuits between wirings, ordeterioration in the withstand voltage of an insulating film.

Further, since most insulating films having a low relative dielectricconstant contain an organic component, the surface of such insulatingfilms is hydrophobic and hence poor in wettability to water. As aresult, dust is easily adsorbed onto the surface of the insulating filmduring the CMP treatment or during the washing after the CMP treatment.Moreover, the dust thus adsorbed cannot be removed, which is one of theproblems preventing wirings from being electrically isolated from eachother. The insulating film having a low relative dielectric constant isalso accompanied with a defect that scratches are more likely to beformed thereon.

BRIEF SUMMARY OF THE INVENTION

A post-CMP treating liquid according to one embodiment of the presentinvention comprises:

-   -   water; and    -   resin particles dispersed in the water and having a functional        group at a surface thereof,    -   the treating liquid exhibiting a polishing rate both of an        insulating film and a conductive film of 10 nm/min or less.

A post-CMP treating liquid according to another embodiment of thepresent invention comprises:

-   -   water;    -   resin particles dispersed in the water; and    -   an additive having a functional group and incorporated in the        water,    -   the treating liquid exhibiting a polishing rate both of an        insulating film and a conductive film of 10 nm/min or less.

A method for manufacturing a semiconductor device according to oneembodiment of the present invention comprises:

-   -   forming an objective film to be treated above a semiconductor        substrate;    -   subjecting the objective film to a polishing treatment to obtain        a polished surface; and    -   treating the polished surface by using a treating liquid        comprising water incorporating resin particles in such a manner        that the polished surface is not substantially polished.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIGS. 1A to 1C are cross-sectional views each illustrating themanufacturing method of a semiconductor device according to oneembodiment of the present invention; and

FIGS. 2A to 2C are cross-sectional views each illustrating themanufacturing method of semiconductor device according to anotherembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Next, embodiments according to the present invention will be explainedin detail.

The present inventors have considered that the removal of dust remainingon the surface of the wiring layer immediately after CMP treatment hasbeen achieved by the combined effect of four fundamental actions, i.e.dissolution, chemical action, mechanical action and surface activity.For example, a treating liquid containing a chelate complex-formingagent for providing chemical action, and a surfactant for effectingsurface activity, both of these components being incorporated into purewater for dissolution, is employed and fed to the surface of a wiringlayer while the surface of the wiring layer is being polished with apolishing cloth, thereby applying a mechanical effect on the residualdust.

On the other hand, it has been found by the present inventors that it ispossible to remove residual materials, such as dust, from the surface ofa fine wiring layer, by performing a sufficient mechanical action on thesurface of the fine wiring layer even if actions such as chemical actionand surface activity are not necessarily applied thereto. Namely, it hasbeen found that the residual materials can be substantially completelyremoved by using the treating liquid according to one embodiment of thepresent invention in which the resin particles stably dispersed in waterand applying a sufficient mechanical action on residual materialsadhered to the surface of a fine wiring layer.

In the embodiments of the present invention, the main object thereof isto remove residual materials from the surfaces both of a wiring layerand an insulating film, so that they are not intended to polish theinsulating film such as SiO₂ and the conductive film such as Cu, Ta,etc. Rather, an objective film to be treated, i.e. the insulating filmand conductive film should not be polished by the treatment using thetreating liquid according to the embodiments of the present invention.Therefore, the polishing rate of the insulating film and conductive filmthat may be achieved by the treatment with the treating liquid accordingto the embodiments of the present invention should be confined to 10nm/min or less. If this polishing rate is 10 nm/min or less irrespectiveof the polishing conditions and of the kind of insulating film andconductive film, it may be deemed that the insulating film andconductive film are substantially not polished, thus achieving theeffects of the embodiments of the present invention.

As for the resin particles, they may made from, for example,polymethylmethacrylate (PMMA), polystyrene, polyethylene, polyethyleneglycol, polyvinyl acetate, polybutadiene, polyisobutylene, polypropyleneand polyoxymethylene. The resin particles may be formed of a singlematerial or may be formed of a combination of two or more materials.

When a polishing cloth is employed in the removal of the residualmaterials, the material for the polishing cloth may be unwoven fabric,sponge, a foamed material or non-foamed material. Any of these materialswould be capable of providing the resin particles with a sufficientmechanical action so as to effectively remove the residual materials.

The resin particles as mentioned above are dispersed in pure water ordeionized water to obtain a treating liquid according to the embodimentsof the present invention. When the resin particles are accompanied by afunctional group, it can be stably dispersed in water. Moreover, due tothe effects of the functional group, the effect of surface activitywould be provided to the resin particles, thus making it possible toenhance the washing effect of the resin particles. It is preferable, inorder to promote the adsorption of the resin particles to the residualmaterials so as to further enhance the washing effect of the resinparticles, to select the functional group whose electric potential inwater is opposite to that of the residual materials.

As explained later, the washing effect of the treating liquid accordingto the embodiments of the present invention can be further enhanced bythe addition of a chelate complex-forming agent or a surfactant. Sincemost of these additives are anionic, the surface of the resin particlesshould preferably be also made anionic in view of stabilizing thedispersion thereof in the treating liquid. Additionally, the anionicresin particles are advantageous as compared with cationic resinparticle in that the safety thereof is higher, that the kind thereof ismore plentiful, and that the cost thereof is cheaper. As for thespecific functional group capable of generating anions (for example,—COO⁻, —SO₃ ⁻) in water, it includes a carboxyl group and sulfonylgroup. Especially, a carboxyl group is more preferable. Incidentally, asfor the functional group capable of generating cations (for example,—NH₃ ⁺) in water, it includes an amino group.

When the functional group exist bonding to the surface of the resinparticles for instance, the functional group is enabled to exhibit thefunction thereof even if the quantity of the functional group is verysmall. Alternatively, it is also possible to separately incorporate anadditive having the functional group into the treating liquid. Theadditive having the functional group may be either anionic or cationic.Specific examples of an anionic additive are, for example,dodecylbenzene sulfonate or the salts thereof, alkyl phosphate or thesalts thereof, dodecyl sulfonate or the salts thereof, and alkenylsuccinate or the salts thereof. A specific example of a cationicadditive is, for example, cetyl ammonium salt, etc. Further, it is alsopossible to employ a nonionic additive such as polyoxyethylene and alkylether. If these additives are separately added to the treating liquid,the content thereof should preferably be in the range of about 0.01 to 5wt % based on the total weight of the treating liquid. If the content ofthese additives falls outside this range, it may be difficult to obtainthe desired effects. Among these additives, dodecylbenzene sulfonate orthe salts thereof are excellent in adsorbability to hydrophobicmaterials since an alkyl chain and benzene ring exist at the hydrophobicsite of a dodecylbenzene sulfonate or the salts thereof. Moreover,because of the fact that sulfonic acid, which is excellent in affinityto water, exists at the hydrophilic site of dodecylbenzene sulfonate orthe salts thereof, dodecylbenzene sulfonate or the salts thereof alsofunction as a surfactant for enhancing the washing effect to wirings.

The primary particle diameter of the resin particles should preferablybe confined to the range of 10 nm to 5,000 nm. If the primary particlediameter of the resin particle falls outside this range, it may becomedifficult to enable the resin particles to exhibit a sufficientmechanical effect. When a polishing cloth is employed, for example,since the surface roughness of a polishing cloth is within the range ofabout 5,000 to 20,000 nm, it is required, in order to remove adheredmatters from the surface of a wiring, to apply a mechanical action by afine textured wiping which is smaller in roughness than that of thesurface of the polishing cloth. Even in the case where a washing memberwhich is not perform conditioning is employed, as in the case of rollwashing or pencil washing, the primary particle diameter of the resinparticles should preferably be not more than 5,000 nm in order torealize an effective mechanical action.

Even if the quantity of the resin particle in the treating liquid is assmall as 0.001 wt % based on the total quantity of the treating liquid,it is possible to realize the effect of removing the adhered matter. Inorder to cope with the semiconductor device of the next generation whosedesign rule of wiring is 0.1 μm or less, the concentration of the resinparticle in the treating liquid should preferably be set to the range of0.1 wt % to 20 wt %. When the concentration of the resin particle is 0.1wt % or more, it becomes possible to turn a hydrophobic surface into asufficiently hydrophilized surface, thereby making it possible togreatly enhance the washing effect of the treating liquid. Further, inorder to stably disperse the resin particles in water so as to enablethe resin particles to sufficiently exhibit the effects thereof, theupper limit of the concentration of resin particle should preferably beconfined to 20 wt %.

If necessary, a chelate complex-forming agent as well as a surfactantmay be added to the treating liquid comprising the resin particle andthe functional group. It is possible, through the addition of thesecomponents, to further enhance the effects of removing theaforementioned adhered matters.

Specific examples of the chelate complex-forming agent are an organicacid such as oxalic acid, citric acid, malonic acid, tartaric acid,malic acid and lactic acid; ammonia; and a basic salt such as ethylenediamine. These chelate complex-forming agents may be incorporated intothe treating liquid at a content of about 0.01 wt % to 1 wt % forinstance. Specific examples of the surfactant are a polyacrylic acid,and polycarboxylic acid, etc., which can be incorporated into thetreating liquid at a content of about 0.001 wt % to 1 wt % for instance.

For the practical use of the treating liquid, the treating liquidprepared as explained above is applied to the surfaces of a wiring layerand of an insulating film after the CMP treatment, and then, amechanical action by using a member such as a polishing cloth, a roll ora pencil is further applied to the surfaces of a wiring layer and of aninsulating film to remove residual material from the surface of a wiringlayer and insulating film, thus obtaining a semiconductor deviceexhibiting excellent electric properties.

Next, one example where a Cu damascene wiring was formed by the methodaccording to one embodiment of the present invention will be explained.

FIGS. 1A to 1C show cross-sectional views each illustrating the methodaccording to one embodiment of the present invention.

First of all, as shown in FIG. 1A, a barrier metal film 105 and a wiringmaterial film 106 are deposited on the surface of a semiconductorsubstrate 100 having semiconductor elements (not shown) formed thereonwith an inorganic insulating film 101 and an insulating laminate films103 and 104 being interposed therebetween.

In the inorganic insulating film 101, a plug 102 formed of tungsten (W)is buried. The laminate insulating film is constituted by a firstinsulating film 103 having a relative dielectric constant of less than2.5, and a second insulating film 104 deposited on the first insulatingfilm 103 and having a relative dielectric constant higher than that ofthe first insulating film 103. The thickness of each of first and secondinsulating films may be 100 nm.

The first insulating film 103 may be formed by using at least oneselected from the group consisting of a film of a compound having asiloxane skeleton such as polysiloxane, hydrogensilsesquioxane,polymethylsiloxane, and methylsilsesquioxane; a film comprising mainlyof an organic resin such as polyarylene ether, polybenzoxazole andpolybenzocyclobutene; and a porous film such as a porous silica film.The first insulating film comprising these materials is fragile.

The second insulating film 104 deposited on the first insulating film103 functions as a cap insulating film and may be formed by using atleast one insulating film having a relative dielectric constant of 2.5or more and selected from the group consisting, for example, of SiC,SiCH, SiCN, SiOC, SiN and SiOCH. The surface of the second insulatingfilm 104 formed of these materials exhibits hydrophobicity.Incidentally, even an insulating film exhibiting hydrophilicity such asa film of SiO, SiOP, SiOF and SION may be afflicted with the problemthat residual matter adheres thereto after the CMP treatment. Thetreating liquid according to the embodiments of the present inventioncan be also suitably employed for treating these insulating films.

The barrier metal film 105 and the wiring material film 106 aredeposited the entire surface of the laminate insulating film afterwiring grooves are formed in the aforementioned laminate insulatingfilm. The barrier metal film 105 may be constituted by a Ta film havinga thickness of 10 nm, and the wiring material film 106 may beconstituted by a Cu film having a thickness of 400 nm.

Incidentally, in the embodiment shown in FIG. 1A, the insulating film onwhich the barrier metal film 105 and the wiring material film 106 isformed, is a laminate structure comprising the first insulating film 103and the second insulating film 104. However, this insulating film may beformed of a single layer of insulating film. The insulating film in thiscase can be formed by using black diamond (Applied Materials Co., Ltd.)for instance. The surface of the second insulating film 104 formed ofthese materials is also exhibits hydrophobicity.

Next, the superfluous portions of the barrier metal film 105 and thewiring material film 106 were removed by CMP to expose the surface ofthe second insulating film 104 as shown in FIG. 1B. This CMP wasperformed in two steps, i.e. the removal of the wiring material film 106(1st polishing), and the removal of the barrier metal film 105 (2ndpolishing). The conditions for this CMP were as follows.

(1st polishing)

-   -   Slurry: CMS7303/7304 (JSR Co., Ltd.)    -   Feeding rate of slurry: 250 cc/min;    -   Polishing pad: IC1000 (tradename; Rodel Nitta Co., Ltd.);    -   Load (DF): 300 gf/cm².

The number of rotation of the carrier and the turntable was both set to100 rpm, and the polishing was continued for one minute.

(2nd polishing)

-   -   Slurry: CMS8301 (JSR Co., Ltd.)    -   Feeding rate of slurry: 200 cc/min;    -   Polishing pad: IC1000 (tradename; Rodel Nitta Co., Ltd.);    -   Load (DF): 300 gf/cm².

The number of rotatiln of the carrier and the turntable was both set to100 rpm, and the polishing was continued for 30 seconds.

As shown in FIG. 1B, residual matter, such as polishing particle 107 andpolish-product material 108 may adhere on the surfaces of the secondinsulating film 104, of the barrier metal film 105 and of the wiringmaterial film 106 immediately after the second polishing.

These adhered materials are removed by washing using the treating liquidaccording to the embodiments of the present invention to obtain a cleansurface as shown in FIG. 1C.

The treating liquids according to the embodiments of the presentinvention were prepared by the following procedures.

EXAMPLE 1

PMMA particles having a carboxyl group on the surface thereof (primaryparticle diameter: 10 nm) were prepared as the resin particles and then,dispersed in pure water at a concentration of 0.001 wt % to prepare thetreating liquid of Example 1.

EXAMPLES 2-6

Various kinds of treating liquid were prepared in the same manner as inExample 1 except that the concentration of the resin particles wasmodified to 0.01 wt %, 0.1 wt %, 1 wt %, 5 wt % and 20 wt %.

EXAMPLE 7

Polystyrene particles having a carboxyl group on the surface thereof(primary particle diameter: 10 nm) were prepared as the resin particlesand then, dispersed in pure water at a concentration of 0.1 wt % toprepare the treating liquid of Example 7.

EXAMPLE 8

Two kinds of resin particles, i.e. polystyrene particle having acarboxyl group on the surface thereof (primary particle diameter: 10nm), and PMMA particles having a carboxyl group on the surface thereof(primary particle diameter: 10 nm) were prepared and then, dispersedrespectively in pure water to prepare the treating liquid of Example 8.Both of two resin particles are dispersed in pure water at aconcentration of 0.05 wt %.

EXAMPLE 9

PMMA particles having a carboxyl group on the surface thereof (primaryparticle diameter: 100 nm) were prepared as a resin particles and then,dispersed in pure water at a concentration of 0.1 wt % to prepare thetreating liquid of Example 9.

EXAMPLES 10 and 11

Two kinds of treating liquid were prepared in the same manner as inExample 9 except that the primary particle diameter of the resinparticles was modified to 1000 nm and 5000 nm, respectively.

EXAMPLE 12

Potassium dodecylbenzene sulfonate was employed as an additive having afunctional group and dissolved in pure water at a concentration of 0.1wt %, and then, PMMA particles (primary particle diameter: 10 nm) as theresin particles were also dispersed in the aforementioned pure water ata concentration of 0.1 wt % to prepare the treating liquid of Example12. In the treating liquid of this example, the functional group was notbonded to the surface of the resin particles but was available from thedodecylbenzene sulfonate.

EXAMPLE 13

Oxalic acid was employed as an organic acid (chelate complex-formingagent) and added, at a concentration of 0.2 wt %, to a treating liquidhaving the same composition as that of Example 3 to prepare the treatingliquid of Example 13.

EXAMPLE 14

Citric acid was employed as an organic acid (chelate complex-formingagent) and added, at a concentration of 0.2 swt %, to a treating liquidhaving the same composition as that of Example 3 to prepare the treatingliquid of Example 14.

EXAMPLE 15

Polyacrylic acid was employed as-a surfactant and added, at aconcentration of 0.05 wt %, to a treating liquid having the samecomposition as that of Example 14 to prepare the treating liquid ofExample 15.

EXAMPLE 16

Polystyrene particles having a sulfonyl group on the surface thereof(primary particle diameter: 10 nm) were prepared as the resin particlesand then, dispersed in pure water at a concentration of 0.1 wt % toprepare the treating liquid of Example 16.

EXAMPLE 17

Polystyrene particles having an amino group on the surface thereof(primary particle diameter: 10 nm) were prepared as the resin particlesand then, dispersed in pure water at a concentration of 0.1 wt % toprepare the treating liquid of Example 17.

EXAMPLE 18

Alkenyl succinate was employed as an additive having a functional groupand dissolved in pure water at a concentration of 0.1 wt %, and then,PMMA particles (primary particle diameter: 10 nm) as the resin particleswere also dispersed in the aforementioned pure water at a concentrationof 0.1 wt % to prepare the treating liquid of Example 18. In thetreating liquid of this example, a carboxyl group as the functionalgroup was not bonded to the surface of the resin particle but wasavailable from the alkenyl succinate.

EXAMPLE 19

Ammonium chloride was employed as an additive having a functional groupand dissolved in pure water at a concentration of 0.1 wt %, and then,PMMA particles (primary particle diameter: 10 nm) as the resin particleswere also dispersed in the aforementioned pure water at a concentrationof 0.1 wt % to prepare the treating liquid of Example 19. In thetreating liquid of this example, an amino group as the functional groupwas not bonded to the surface of the resin particle but was availablefrom the ammonium chloride.

By using the treating liquids prepared in Examples 1 to 19, the surfaceconstructed as shown in FIG. 1B was washed. This washing was performedwhile the treating liquid was supplied to the polishing cloth (RodelNitta Co., Ltd.) having a surface roughness of about 10,000 nm with thepolishing cloth being kept contacted with the treating surface for about15 to 60 seconds so as to wipe the treating surface with the polishingcloth under the following conditions. In this case, the treating surfaceis constituted by the surface of the second insulating film 104 and ofthe wiring material film 106.

-   -   Flow rate of washing liquid: 300 cc/min;    -   Load: 300 gf/cm².

The number of rotations of the carrier and the turntable was both set to100 rpm.

Since it becomes difficult to remove residual materials once thetreating surface is dried out, the washing should preferably beperformed while the treating surface is in a wet state. Namely, thewashing should preferably be continuously performed after finishing thesecond polishing and by using the same apparatus.

Incidentally, instead of the washing using a polishing cloth, it is alsopossible to employ roll washing or pencil washing.

The surface constructed as shown in FIG. 1B was washed in the samemanner as described above except that the following treating liquidswere employed, which were defined as Comparative Examples 1 to 3.

Comparative Example 1 Pure Water

Comparative Example 2

Pure Water Containing Oxalic Acid (0.2 wt %). Comparative Example 3 PureWater Containing Oxalic Acid (0.2 wt %) and Polyacrylic Acid (0.05 wt%).

Incidentally, Comparative Example 3 corresponds to the conventionaltreating liquid.

After the washing treatment, the wirings (line/space: 0.08 μm/0.08 μm)obtained were investigated with respect to the yield regarding theshort-circuit of wirings and the I-V characteristics of the insulatingfilm were measured based on the values of leak current (applied electricfield: 1 MV/cm), the results being summarized in the following Table 1.TABLE 1 Yield regarding Leak the short-circuit current of the wirings(%) (nA) Example 1 90 11 Example 2 96 2 Example 3 96 3 Example 4 97 4Example 5 97 4 Example 6 96 2 Example 7 96 4 Example 8 97 3 Example 9 975 Example 10 96 7 Example 11 95 8 Example 12 96 3 Example 13 99 0.5Example 14 100 0.4 Example 15 100 0.2 Example 16 97 2 Example 17 96 2Example 18 97 2 Example 19 97 2 Comp. Example 1 65 6548 Comp. Example 272 873 Comp. Example 3 75 664

As shown in Table 1, by washing the treating surface with a treatingliquid containing the resin particle and the functional group (Examples1 to 19), the electric characteristics of the semiconductor devicesobtained were improved. More specifically, the yield regarding theshort-circuit of wiring was increased to 90% or more, and the leakcurrent was minimized to 11 nA or less. Incidentally, in all of theseExamples, the polishing rate of the wiring material film 106 was about1.5 nm/min, and the polishing rate of the second insulating film 104 wasabout 1 nm/min.

It was assumed from these results that the treating liquids containingthe resin particles were capable of applying a mechanical action to thehydrophobic insulating film that was fragile and low in relativedielectric constant without imposing an excessive load on the insulatingfilm, thereby making it possible, without causing the generation ofscratches, to effectively remove the dust and residual matter that maygive rise to the deterioration of electric characteristics of thesemiconductor devices.

Incidentally, in the case of the semiconductor device of the nextgeneration where the design rule is 0.1 μm, it is required that theyield regarding the short-circuit of wiring is 95% or more, and the leakcurrent is confined to less than 10 nA. It is now possible, through theemployment of the treating liquid containing resin particles at aconcentration of 0.01 wt % or more (Examples 2 to 19), to cope with thedesign rule of the next generation.

By contrast, in the Comparative Examples where the treating liquidcontaining no resin particles, the yield regarding the short-circuit ofwiring was at most 75%, and the leak current was as high as 6500 mA.Namely, it was assumed that since dust and the like could not becompletely removed, it was only possible to achieve such a lowperformance.

Although the embodiments of the present invention have been explainedtaking the treatment after a Cu-CMP treatment as an example, the presentinvention is not limited to such embodiments. Namely, the treatingliquid containing resin particles according to the present invention isalso applicable to the formation of buried electrodes, wirings and plugswhere Al, W and polysilicone are employed, to obtain almost the sameeffects as explained above. Further, the treating liquid of theembodiment of the present invention is also useful for the posttreatment performed after the CMP treatment of a SiO₂ layer employed asan insulating film deposited on the surface of wirings, so that it ispossible, through the employment of the treating liquid of theembodiment of the present invention, to effectively perform the washingof the SiO₂ layer to obtain a clean surface.

Furthermore, the treatment by using the treating liquid according to theembodiments of the present invention is also applicable to the formationof STI (Shallow Trench Isolation).

The procedures for the formation of this STI will be explained withreference to FIGS. 2A to 2C.

First of all, as shown in FIG. 2A, a groove is formed in a semiconductorsubstrate 200 having a CMP stopper film 201 formed thereon, and then, aninsulating film 202 is deposited the entire resultant substrate. In thiscase, SiN can be employed as the CMP stopper film 201. As for theinsulating film 202, it is possible to employ a SiO₂ film which can beformed by HDP (High Density Plasma) method. Alternatively, carbon (C)can be also employed as the CMP stopper film 201, and a coat typeinsulating film such as an organic SOG can be also employed as theinsulating film 202.

Next, a superfluous portion of the insulating film 202 is removed by CMPto expose the surface of the CMP stopper film 201 as shown in FIG. 2B.The conditions for this CMP were as follows.

-   -   Slurry: 0.5 wt % ceria particle        -   +0.01 wt % polyacrylic acid        -   +pure water (pH: 6);    -   Flow rate of slurry: 300 cc/min;    -   Polishing pad: IC1000 (tradename; Rodel Nitta Co., Ltd.);    -   Load (DF): 300 gf/cm².

The number of rotations of the carrier and the turntable was both set to100 rpm, and the polishing was continued for one minute.

C and SiN used as a material for the CMP stopper film 201 arehydrophobic in most cases and the ζ potential thereof is considered tobe isoelectric point. Therefore, polishing particles 203 may be adhereto the CMP stopper film 201 immediately after the polishing as shown inFIG. 2B.

These adhered matters can be washed out and removed by using thetreating liquid according the embodiments of the present invention, thusobtaining a clean surface as shown in FIG. 2C.

The treating liquid according to this embodiment of the presentinvention was prepared by the procedures as described below.

EXAMPLE 20

PMMA particles having an amino group on the surface thereof (primaryparticle diameter: 50 nm) were prepared as the resin particles and then,dispersed in pure water at a concentration of 0.05 wt %, and polyacrylicacid was also added as a surfactant to the pure water at a concentrationof 0.05 wt % to prepare the treating liquid of Example 20.

By using the treating liquid prepared in Example 20, the surfaceconstructed as shown in FIG. 2B was washed. This washing was performedfor 60 seconds by using a roll (Ebara Co., Ltd.) and by feeding thetreating liquid to the surface of the roll at a flow rate of 1000 cc/minwhile rotating the roll at a rotational speed of 100 rpm. Thereafter,the resultant surface was further washed for 60 seconds by feeing purewater at a flow rate of 1000 cc/min while rotating the roll at arotational speed of 100 rpm. As explained above, the washing treatmentshould preferably be performed against the wet surface obtainedimmediately after finishing the polishing.

Additionally, the surface constructed as shown in FIG. 2B was washed inthe same manner as described above except that pure water containingpolyacrylic acid (0.05 wt %) was employed, which was defined asComparative Example 4.

After these washing treatments, the residual polishing particles thatmay be adsorbed onto the surface of the CMP stopper film 201 wereexamined by using a defect-evaluation apparatus (KLA Tencol Co., Ltd.).As a result, in the case of Comparative Example 4, the number of theresidual polishing particles adhered to the washed surface was found1000/cm² or more. Whereas, in the case of Example 20, there was noresidual polishing particles. It was confirmed from these results thatthe residual polishing particles adhered onto the surface of the CMPstopper film 201 after the polishing were substantially completelyremoved from the surface of the CMP stopper film 201 by the washingusing the treating liquid of this embodiment of the present invention.

Incidentally, the polishing rate of the insulating film 202 by thetreating liquid of Example 20 was about 1 nm/min, and the polishing rateof the CMP stopper film 201 was about 0.5 nm/min.

The treating liquid according to the embodiments of the presentinvention is also applicable to washing treatments other than thepost-treatment after the CMP treatment. For example, the treating liquidadditionally containing an organic acid is also applicable to theremoval of dust from an insulating film formed by plasma CVD, or to theremoval of heavy metals remaining on the surface of silicon substrate,thereby making it possible to obtain a clean surface.

As explained above, it is possible, according to the embodiments of thepresent invention, to provide a post-CMP treating liquid, which iscapable of effectively removing residual matters adhered to the surfacesof wiring layer or of insulating film. There is also provided, accordingto the embodiments of the present invention, a method for manufacturinga semiconductor device where the aforementioned post-CMP treating liquidis employed.

Since it is also possible, according to the present invention, tomanufacture a semiconductor device having wirings 0.1 μm in design rule,thus exhibiting a high performance and a high processing speed, thepresent invention is very valuable from an industrial viewpoint.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention is its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1. A post-CMP treating liquid comprising: water; and resin particlesdispersed in said water and having a functional group at a surfacethereof, said treating liquid exhibiting a polishing rate each of anSiO₂ film, Cu film and Ta film of 10 nm/min or less.
 2. The post-CMPtreating liquid according to claim 1, wherein said resin particlescomprises at least one selected from the group consisting ofpolymethylmethacrylate, polystyrene, polyethylene, polyethylene glycol,polyvinyl acetate, polybutadiene, polyisobutylene, polypropylene andpolyoxymethylene.
 3. The post-CMP treating liquid according to claim 1,wherein said functional group comprises at least one selected from thegroup consisting of a carboxyl group, an amino group and a sulfonylgroup.
 4. The post-CMP treating liquid according to claim 1, wherein theprimary particles diameter of said resin particles is in the range of 10nm to 5000 nm.
 5. The post-CMP treating liquid according to claim 1,wherein a concentration of said resin particles is in the range of 0.01wt % to 20 wt %.
 6. The post-CMP treating liquid according to claim 1,further comprising at least one of a chelate complex-forming agent and asurfactant.
 7. A post-CMP treating liquid comprising: water; resinparticles dispersed in said water; and an additive having a functionalgroup and incorporated in said water, said treating liquid exhibiting apolishing rate each of an SiO₂ film, Cu film and Ta film of 10 nm/min orless.
 8. The post-CMP treating liquid according to claim 7, wherein saidresin particles comprises at least one selected from the groupconsisting of polymethylmethacrylate, polystyrene, polyethylene,polyethylene glycol, polyvinyl acetate, polybutadiene, polyisobutylene,polypropylene and polyoxymethylene.
 9. The post-CMP treating liquidaccording to claim 7, wherein said functional group comprises at leastone selected from the group consisting of a carboxyl group, an aminogroup and a sulfonyl group.
 10. The post-CMP treating liquid accordingto claim 7, wherein the primary particles diameter of the resinparticles is in the range of 10 nm to 5000 nm.
 11. The post-CMP treatingliquid according to claim 7, wherein a concentration of said resinparticles is in the range of 0.01 wt % to 20 wt %.
 12. The post-CMPtreating liquid according to claim 7, further comprising at least one ofa chelate complex-forming agent and a surfactant. 13-23. (canceled) 24.The post-CMP treating liquid according to claim 1, wherein the treatingliquid exhibits a polishing of an insulating film formed of at least oneselected from the group consisting of SiC, SiCH, SiCN, SiOC, SiN, SiOCH,SiO, SiOP, SiOF and SiON of 10 nm/min or less.
 25. The post-CMP treatingliquid according to claim 1, wherein the treating liquid exhibits apolishing rate of a conductive film formed of at least one selected fromthe group consisting of Al, W and polysilicone of 10 nm/min or less. 26.The post-CMP treating liquid according to claim 7, wherein the treatingliquid exhibits a polishing of an insulating film formed of at least oneselected from the group consisting of SiC, SiCH, SiCN, SiOC, SiN, SiOCH,SiO, SiOP, SiOF and SiON of 10 nm/min or less.
 27. The post-CMP treatingliquid according to claim 7, wherein the treating liquid exhibits apolishing rate of a conductive film formed of at least one selected fromthe group consisting of Al, W and polysilicone of 10 nm/min or less.